CN106299289A - The preparation method of a kind of cobalt acid zinc/guar gum/Pt/Polypyrrole composite material and application - Google Patents
The preparation method of a kind of cobalt acid zinc/guar gum/Pt/Polypyrrole composite material and application Download PDFInfo
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- CN106299289A CN106299289A CN201610815148.XA CN201610815148A CN106299289A CN 106299289 A CN106299289 A CN 106299289A CN 201610815148 A CN201610815148 A CN 201610815148A CN 106299289 A CN106299289 A CN 106299289A
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- guar gum
- acid zinc
- cobalt acid
- polypyrrole
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- 229920002907 Guar gum Polymers 0.000 title claims abstract description 47
- 229960002154 guar gum Drugs 0.000 title claims abstract description 47
- 235000010417 guar gum Nutrition 0.000 title claims abstract description 47
- 239000000665 guar gum Substances 0.000 title claims abstract description 47
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 45
- 239000010941 cobalt Substances 0.000 title claims abstract description 45
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 45
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 239000002253 acid Substances 0.000 title claims abstract description 42
- 239000011701 zinc Substances 0.000 title claims abstract description 42
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 42
- 239000002131 composite material Substances 0.000 title claims abstract description 26
- 229920000128 polypyrrole Polymers 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000004146 energy storage Methods 0.000 claims abstract description 5
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 22
- 239000000178 monomer Substances 0.000 claims description 14
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims description 8
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims description 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- 229940068041 phytic acid Drugs 0.000 claims description 8
- 235000002949 phytic acid Nutrition 0.000 claims description 8
- 239000000467 phytic acid Substances 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 5
- 230000005611 electricity Effects 0.000 claims description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 17
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 17
- 239000004005 microsphere Substances 0.000 abstract description 9
- 229920001940 conductive polymer Polymers 0.000 abstract description 8
- 238000006116 polymerization reaction Methods 0.000 abstract description 7
- 238000011065 in-situ storage Methods 0.000 abstract description 6
- 230000007246 mechanism Effects 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- 238000005253 cladding Methods 0.000 abstract description 3
- 230000004044 response Effects 0.000 abstract description 3
- 230000004087 circulation Effects 0.000 description 6
- 239000007772 electrode material Substances 0.000 description 5
- 238000013019 agitation Methods 0.000 description 4
- 239000002322 conducting polymer Substances 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 4
- 238000000643 oven drying Methods 0.000 description 4
- 239000011149 active material Substances 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002848 electrochemical method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910003119 ZnCo2O4 Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 206010011224 Cough Diseases 0.000 description 1
- 244000303965 Cyamopsis psoralioides Species 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 229910003168 MnCo2O4 Inorganic materials 0.000 description 1
- 229910005949 NiCo2O4 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/48—Conductive polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H01M4/602—Polymers
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention provides the preparation method and application of a kind of cobalt acid zinc/guar gum/Pt/Polypyrrole composite material, the method using in-situ polymerization, utilize guar gum to strengthen polypyrrole Signa Gel carry out hollow cobalt acid zinc microsphere cladding thus improve the mechanical strength of conductive polymer gel, enhance the stability of material.Mechanism and enhancement mechanism is controlled by the consumption and response time controlling guar gum.Composite capacity after circulating 100 times can be stablized at 432mAh g‑1.The method effectively improves cobalt base oxide and the volumetric expansion in charge and discharge process of conductive polymer gel composite, the problem of easy fracture in conventional lithium ion battery negative material, improves cyclical stability.Cobalt acid zinc/guar gum/Pt/Polypyrrole composite material is with a wide range of applications in terms of the cycle life improving lithium ion battery negative material, also apply be applicable to the energy storage devices such as ultracapacitor simultaneously, and is hopeful to be applied to the fields such as sensor.
Description
Technical field
The present invention provides preparation and the application of a kind of organic-inorganic nanocomposite, i.e. cobalt acid zinc/guar gum/poly-
The preparation method of pyrroles's composite and application.
Background technology
In 21 century, global energy shortage is a severe problem.Some green energy resources, such as solar energy, wind energy, waterpower
Generating etc. is replacing Fossil fuel.Electrochemical energy because its energy density and energy conversion efficiency are high, can arbitrarily assemble and move
The advantages such as dynamic, noise-less pollution, have become as focus of concern.Lithium-ion battery systems is the secondary cell of a new generation,
Owing to having high-energy-density and relatively simple reaction mechanism, widely should obtain in portable type electronic product field
With.Along with development, the demand of the aspect of performances such as the energy density of lithium electricity, cycle life, safety is needed into one
The raising of step.
At present, as the Co of electrode material of lithium battery spinel structure3O4Owing to theoretical capacity is up to 890mAh/g, it is approximately
2～3 times of graphite cathode material, and there is the features such as high cyclical stability and long-life, in catalyst, sensor, electrochemistry
The field such as device and lithium ion battery electrode material is all widely used and studies.But the toxicity and expensive due to it
Limit its application etc. shortcoming, promote people to continually develop new substitution material, such as NiCo2O4、MnCo2O4、ZnCo2O4Deng.
ZnCo2O4Theoretical capacity be up to 976mAh/g, and with its relatively low price and safety it is considered to be a kind of preferably substitute
Material.
Conducting polymer due to its good electric conductivity, excellent processing characteristics and low cost by extensive coated particle system
Standby negative material.Conducting polymer has buffer agent and the conductive agent effect of active material concurrently, can be prevented effectively from traditional electrode by
The capacity fade problem caused in the interpolation of the non-active material such as conductive agent, binding agent.Common conducting polymer such as polyphenyl
Amine, polypyrrole and polythiophene etc., have been widely used for the structural support system of clad or metal and metal-oxide, significantly
Improve the chemical property of electrode.May significantly improve the electric conductivity of electrode, improve electrode specific capacity and cyclical stability.
But conducting polymer always suffers in charge and discharge process, and mechanical strength is low, be easily broken off the puzzlements such as deformation at certain
Its commercial applications is constrained in the degree of kind.Guar gum is a kind of macromole Natural hydrophilic colloid, and itself is containing great amount of hydroxy group,
Sudhakar et al. demonstrates lithium ion and can move at guar gum hapto, is similar to lithium ion in polyethylene oxide
Transmission.Hydrogen bond and covalent bond can be formed with the amino in polyaniline, thus the intensity of polypyrrole gel can be obviously enhanced, it is possible to
More preferably improve the reunion in long-term cyclic process of the cobalt acid Zinc material and volumetric expansion problem.In addition, guar gum is distinctive viscous
Property alternative adhesive PVDF, improve active substance content.
Summary of the invention
The invention provides the preparation method of a kind of cobalt acid zinc/guar gum/Pt/Polypyrrole composite material.Use chemical in situ
The method of polymerization, the outer surface that the polypyrrole gel that guar gum strengthens is coated on cobalt acid zinc hollow ball obtains a kind of enhancing machine
The composite high-molecular polymeric material of tool performance.The composite of preparation is applied to lithium ion battery negative material, can be effectively improved
Cobalt acid zinc/polypyrrole material problem such as easy fracture, deformation in charge and discharge process, the machinery substantially increasing composite is strong
Degree.And utilize the distinctive viscosity of guar gum, without binding agent during assembled battery, improve the content of active substance.
Technical scheme is as follows:
1) guar gum powder is scattered in deionized water it is made into the solution that mass fraction is 0.3～0.5%, by Guar
Many glue and cobalt acid zinc mass ratio are that the ratio of 1:8～10 adds cobalt acid zinc Hollow sphere particles, stir and obtain suspension in 2～4 hours；
2) by suspension as under ice bath, pyrrole monomer and phytic acid are joined in solution, makes the quality of pyrrole monomer divide
Number is 0.01～0.02%, stirs 1～2 hour under ice bath；It is subsequently added Ammonium persulfate. so that it is with the mass ratio of pyrrole monomer be
1:0.5～1, stirs 2～5 minutes；By obtaining after the product distilled water wash of gained, cobalt acid zinc/guar gum/polypyrrole is multiple
Condensation material.
Wherein optimum condition is as follows:
Guar gum liquid quality fraction is 0.4～0.5%.
The mass fraction of pyrrole monomer is 0.015～0.02%.
Guar gum and cobalt acid zinc mass ratio are 1:9～10.
Pyrrole monomer, phytic acid are with volume ratio as 4:1～2.
The cobalt acid zinc/guar gum/Pt/Polypyrrole composite material of the present invention is applied to the energy storage devices such as lithium electricity；And can answer
For sensor.
The cobalt acid zinc/guar gum/Pt/Polypyrrole composite material of the present invention may replace Co with its low cost and hypotoxicity3O4Negative
Pole material, is widely used in the negative material of lithium ion battery, can also be applied to the energy storage devices such as ultracapacitor simultaneously.Tool
Body application only the Copper Foil scribbling active electrode material prepared need to be cut to a diameter of 8mm Copper Foil several directly as electrode
Materials for later use.Electro-chemical test uses button cell system (CR2032), with cobalt acid zinc/guar gum/Pt/Polypyrrole composite material
For working electrode, electrode material and carbon black mass ratio for 9:1, uses lithium metal as to electrode, and barrier film uses Colgard-
2300 lithium ion battery separators, electrolyte system is 1mol/L LiPF6/EC+DMC+EMC (volume ratio 1:1:1).
Compared with other materials, the hollow cobalt acid zinc of the guar gum prepared by the present invention/polypyrrole gel cladding is combined
Material, is evenly coated, and experimental technique is simple, and experiment condition easily reaches, and effectively improves the most prepared cobalt acid zinc/poly-pyrrole
Cough up Signa Gel easy fracture in composite, broken shortcoming.The viscosity simultaneously utilizing guar gum self may replace binding agent
Effect, thus can realize adhesive-free lithium electricity assembling.Carry as lithium ion battery negative material for cobalt base oxide material
Supply a kind of new research method.
Accompanying drawing explanation
Fig. 1 be hollow cobalt acid zinc micro-sphere material sample scanning electron microscope (SEM) photograph.
Fig. 2 is the scanning electron microscope (SEM) photograph of the cobalt acid zinc/guar gum/Pt/Polypyrrole composite material sample of embodiment 1 preparation.Fig. 3
Scanning electron microscope (SEM) photograph for the cobalt acid zinc/guar gum/Pt/Polypyrrole composite material sample of embodiment 3 preparation.Fig. 4 is that embodiment 4 is made
The scanning electron microscope (SEM) photograph of standby cobalt acid zinc/guar gum/Pt/Polypyrrole composite material sample.Fig. 5 be embodiment 3 preparation cobalt acid zinc/
100 cyclic curves of guar gum/Pt/Polypyrrole composite material sample.
Detailed description of the invention
Raw material used in the embodiment of the present invention is commercial products, and purity is analytical pure.
The pattern of granule prepared by the present invention passes through transmission electron microscope photo (TEM), scanning electron microscope (SEM)
Display, uses Japan's JEOL type transmission electron microscope, Japan's Hitachi S4800 type scanning electron microscope, uses three electricity
Pole test system carries out electro-chemical test to sample.
Example 1:
Method initially with in-situ polymerization prepares hollow cobalt acid zinc microsphere.
Measure guar gum powder 10mg with electronic balance to be scattered in the deionized water of 3ml, stir under magnetic stirring apparatus
Mix.Measure hollow cobalt acid zinc microsphere 80mg to be slowly added in solution, continuous mechanical agitation 2 hours.By the suspension after stirring
As under ice bath, pyrrole monomer 40 μ L, phytic acid 10 μ L are joined in solution, stir 1 hour under ice bath.It is subsequently added persulfuric acid
Ammonium 40mg, stirs 2 minutes.Question response terminates, and is separated by solution centrifugal, with distilled water wash 3 times, finally puts oven drying standby
With.
Utilize scanning electron microscope that prepared Product samples is carried out morphology observation, can be seen that it from Figure of description 2
Less for porous spherical structure and covering amount.This product is applied to lithium ion battery negative material, and assembled battery carries out electrification
Learning and characterize, after battery has carried out 100 circulations, battery capacity is by 950mAh g-1Decay to 405mAh g-1, cyclical stability
It is significantly increased relative to not using guar gum.
Example 2:
Method initially with in-situ polymerization prepares hollow cobalt acid zinc microsphere.
Measure guar gum powder 10mg with electronic balance to be scattered in the deionized water of 3ml, stir under magnetic stirring apparatus
Mix.Measure hollow cobalt acid zinc microsphere 90mg to be slowly added in solution, continuous mechanical agitation 2 hours.By the suspension after stirring
As under ice bath, pyrrole monomer 45 μ L, phytic acid 12 μ L are joined in solution, stir 1 hour under ice bath.It is subsequently added persulfuric acid
Ammonium 42mg, stirs 2 minutes.Question response terminates, and is separated by solution centrifugal, with distilled water wash 3 times, finally puts oven drying standby
With.
Utilize scanning electron microscope that prepared Product samples is carried out morphology observation, it can be seen that it is porous spherical structure
And covering amount is less.This product is applied to lithium ion battery negative material, and assembled battery carries out electrochemical Characterization, when battery enters
Having gone after 100 circulations, battery capacity is by 950mAh g-1Decay to 408mAh g-1, cyclical stability is preferable.
Example 3:
Method initially with in-situ polymerization prepares hollow cobalt acid zinc microsphere
Measure guar gum powder 10mg with electronic balance to be scattered in the deionized water of 3ml, stir under magnetic stirring apparatus
Mix.Measure the hollow cobalt micro-95mg of acid zinc to be slowly added in solution, continuous mechanical agitation 3 hours.
By the suspension after stirring as under ice bath, pyrrole monomer 47 μ L, phytic acid 15 μ L are joined in solution, under ice bath
Stir 1 hour.It is subsequently added Ammonium persulfate. 45mg, stirs 3 minutes.Solution centrifugal is separated, with distilled water wash 4 times, finally
Put oven drying standby.
Utilize scanning electron microscope that prepared Product samples is carried out morphology observation, can be seen that it from Figure of description 3
For porous spherical structure and be evenly coated.This product is applied to lithium ion battery negative material, and assembled battery carries out electrochemistry
Characterizing, after battery has carried out 100 circulations, battery capacity is by 950mAh g-1Decay to 432mAh g-1, cyclical stability is relatively
Good.
Example 4:
Method initially with in-situ polymerization prepares hollow cobalt acid zinc microsphere
Measure guar gum powder 10mg by electronic balance amount to be scattered in the deionized water of 3ml, under magnetic stirring apparatus
Stirring.Measure the hollow cobalt micro-100mg of acid zinc to be slowly added in solution, continuous mechanical agitation 2 hours.
By the suspension after stirring as under ice bath, pyrrole monomer 50 μ L, phytic acid 18 μ L are joined in solution, under ice bath
Stir 2 hours.It is subsequently added Ammonium persulfate. 50mg, stirs 5 minutes.Solution centrifugal is separated, with distilled water wash 4 times, finally
Put oven drying standby.
Utilize scanning electron microscope that prepared Product samples is carried out morphology observation, can be seen that bag from Figure of description 4
The chondritic that coating is thicker.This product is applied to lithium ion battery negative material, and assembled battery carries out electrochemical Characterization,
After battery has carried out 100 circulations, battery capacity is by 950mAh g-1Decay to 385mAh g-1, cyclical stability is the most relative
Guar gum is not used to increase.
By these three example it can be seen that guar gum add to strengthen system cycle performance important role.
Guar gum consumption is the most crucial.If consumption is very few, crosslink density is relatively low, and reinforced effects is inconspicuous.If guar gum content
Too much, then the gel being coated on nano-particle is the thickest, the capacity making active material reduces.When consumption is suitable, gained
To product grain be uniformly dispersed.During as negative material, its capability retention is higher, and stable circulation performance has obtained bigger
Improve.
This product is applied to lithium ion battery negative material, when assembled battery carries out electrochemical Characterization, is not required to add and glues
Tie agent thus improve the content of active substance.Battery carried out 100 times circulation after battery capacity by 950mAh g-1Decay to
432mAh·g-1, capability retention is preferable, and electrode cycle stability is significantly improved.
The invention provides the preparation method and application of a kind of cobalt acid zinc/guar gum/Pt/Polypyrrole composite material, use former
The method of position polymerization, utilizes guar gum to improve to strengthen polypyrrole Signa Gel and carry out the cladding of hollow cobalt acid zinc microsphere
The mechanical strength of conductive polymer gel, enhances the stability of material.During by controlling the consumption of guar gum and reacting
Between control mechanism and enhancement mechanism.Composite capacity after circulating 100 times can be stablized at 432mAh g-1.The method is effectively improved
Cobalt base oxide and conductive polymer gel composite body in charge and discharge process in conventional lithium ion battery negative material
Long-pending expansion, the problem of easy fracture, improve cyclical stability.Cobalt acid zinc/guar gum/Pt/Polypyrrole composite material is improving lithium ion
The cycle life aspect of cell negative electrode material is with a wide range of applications, and also apply be applicable to the energy storage such as ultracapacitor simultaneously and sets
Standby, and be hopeful to be applied to the fields such as sensor.
Above example is only to be lifted by the explanation present invention, and protection scope of the present invention is not limited to this.The art
The equivalent done on the basis of the present invention of technical staff substitute and conversion, all within protection scope of the present invention.
Claims (7)
1. the preparation method of cobalt acid zinc/guar gum/Pt/Polypyrrole composite material；It is characterized in that step is as follows:
1) guar gum powder is scattered in deionized water it is made into the solution that mass fraction is 0.3～0.5%, by guar gum
Add cobalt acid zinc Hollow sphere particles with the ratio that cobalt acid zinc mass ratio is 1:8～10, stir and obtain suspension in 2～4 hours；
2) by suspension as under ice bath, joining in solution by pyrrole monomer and phytic acid, the mass fraction making pyrrole monomer is
0.01～0.02%, stir 1～2 hour under ice bath；It is subsequently added Ammonium persulfate. so that it is be 1 with the mass ratio of pyrrole monomer:
0.5～1, stir 2～5 minutes；It is combined obtaining cobalt acid zinc/guar gum/polypyrrole after the product distilled water wash of gained
Material.
2. the method for claim 1, is characterized in that guar gum liquid quality fraction is 0.4～0.5%.
3. the method for claim 1, is characterized in that the mass fraction of pyrrole monomer is 0.015～0.02%.
4. the method for claim 1, is characterized in that guar gum and cobalt acid zinc mass ratio are 1:9～10.
5. the method for claim 1, is characterized in that pyrrole monomer, phytic acid are with volume ratio as 4:1～2.
6. cobalt acid zinc/guar gum/Pt/Polypyrrole composite material is applied to lithium electricity energy storage device.
7. cobalt acid zinc/guar gum/Pt/Polypyrrole composite material is applied to sensor.
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| CN108538631A (en) * | 2018-04-12 | 2018-09-14 | 江苏大学 | Solvent heat-in-situ oxidizing-polymerizing method prepares method and the application of Ni-based cobalt acid magnesium combination electrode material |
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